Micro-Raman and photoluminescence study of urchin-like ZnO structure assembled with nanorods synthesized by hydrothermal method

Urchin-like ZnO structures assembled with nanorods have been synthesized by cetyltrimethylammonium bromide-assisted hydrothermal method. The as-obtained products were characterized by powder X-ray diffraction, field-emission scanning electron microscopy for the study of crystal structure and morphology. The ZnO urchin is constructed of well-assembled nanorods of length ~3 μm range and diameter ~20 nm. Micro-Raman study shows characteristic Raman-active mode of hexagonal ZnO at 439 cm⁻¹ and also mode related to defects at ~581 cm⁻¹. The ZnO urchin assembled with nanorods possessed band edge emission at 3.085 eV and defect related visible emission at 2.97, 2.57, and 2.36 eV.     

Co doped ZnO nanowires as visible light photocatalysts

High aspect ratio cobalt doped ZnO nanowires showing strong photocatalytic activity and moderate ferromagnetic behaviour were successfully synthesized using a solvothermal method and characterized by scanning electron microscopy (SEM), X-ray powder diffraction (XRD), X-ray photoelectron spectroscopy (XPS), X-ray absorption spectroscopy (XAS), vibrating sample magnetometry (VSM) and UV–visible absorption spectroscopy. The photocatalytic activities evaluated for visible light driven degradation of an aqueous methylene orange (MO) solution were higher than for Co doped ZnO nanoparticles at the same doping level and synthesized by the same synthesis route. The rate constant for MO visible light photocatalytic degradation was 1.9·10⁻³ min⁻¹ in case of nanoparticles and 4.2·10⁻³ min⁻¹ in case of nanowires. We observe strongly enhanced visible light photocatalytic activity for moderate Co doping levels, with an optimum at a composition of Zn_0.95Co_0.05O. The enhanced photocatalytic activities of Co doped ZnO nanowires were attributed to the combined effects of enhanced visible light absorption at the Co sites in ZnO nanowires, and improved separation efficiency of photogenerated charge carriers at optimal Co doping.     

Synthesis and properties of delafossite CuAlO<Subscript>2</Subscript> nanowires

Ultra-long and uniform CuAlO₂ nanowires were successfully synthesized within a porous anodic aluminum oxide template by means of sol–gel method at 900 °C. The results of X-Ray diffraction indicate that the obtained CuAlO₂ nanowires have a single delafossite structure. The scanning electron microscopy and transmission electron microscopy show that the CuAlO₂ nanowires have a uniform diameter with about 50 nm and a length up to 10 μm. Room-temperature photoluminescence measurement of nanowires exhibits an ultraviolet near-band-edge emission around 350 nm (3.54 eV).     

Synthesis and characterization of ZnO nanowires by thermal oxidation of Zn thin films at various temperatures

In this research high-quality zinc oxide (ZnO) nanowires have been synthesized by thermal oxidation of metallic Zn thin films. Metallic Zn films with thicknesses of 250 nm have been deposited on a glass substrate by the PVD technique. The deposited zinc thin films were oxidized in air at various temperatures ranging between 450 °C to 650 °C. Surface morphology, structural and optical properties of the ZnO nanowires were examined by scanning electron microscope (SEM), X-ray diffraction (XRD), energy dispersive X-ray (EDX) and photoluminescence (PL) measurements. XRD analysis demonstrated that the ZnO nanowires has a wurtzite structure with orientation of (002), and the nanowires prepared at 600 °C has a better crystalline quality than samples prepared at other temperatures. SEM results indicate that by increasing the oxidation temperature, the dimensions of the ZnO nanowires increase. The optimum temperature for synthesizing high density, ZnO nanowires was determined to be 600 °C. EDX results revealed that only Zn and O are present in the samples, indicating a pure ZnO composition. The PL spectra of as-synthesized nanowires exhibited a strong UV emission and a relatively weak green emission.     

Diluted magnetic semiconductor properties in Zn<Subscript>1−x</Subscript>Cu<Subscript>x</Subscript>O nanoparticles synthesized by sol gel route

Nanoparticles of ZnO:Cu Diluted Magnetic Semiconductor (DMS) are prepared using sol gel method. The structural, optical and EPR properties of them are investigated. The XRD patterns of them show the formation of polycrystalline and hexagonal wurtzite structure without any secondary phase formation. The average size of particles ranges from 14 to 19 nm. In the optical absorption study of the samples, a red shit of optical band edge and a narrowing of the optical band gap are observed when Cu concentration is increased. The PL measurements illustrate 392 nm UV radiation of the near band-edge emissions of ZnO, blue emission at 450 nm and orange emission at 628 nm. The cause of decrease in intensity of these emission lines is the sincerely enhanced non-radiative transitions when Cu is doped in ZnO. EPR measurements provide substantial evidence for the presence of defect states and enhancement of exchange interaction.     

A simple route to obtain TiO2 nanowires by the sol–gel method

In this work, titanium dioxide (TiO₂) nanowires were synthesized by the sol–gel method, without using any kind of templates, instead of that acetic acid was used as morphological modifier. In order to control crystalline phases and crystal size, TiO₂ was calcinated at 400, 500 and 600 °C during 1 h. The resulting morphology was nanowires, which diameter was maintained constant after calcination at different temperature (about 76 nm). Moreover, crystalline phases in order of predominance were anatase, anatase–rutile and rutile–anatase at 400, 500 and 600 °C, respectively. Additionally, the crystallite size increases with respect to temperature from 13 to 75 nm.     

Synthesis and Characterization of TiO2 Doped ZnO Microtubes

The TiO₂-doped ZnO microtubes have been successfully fabricated via a wet chemicalmethod, using zinc chloride and titanium sulphate as the starting materials. The as-synthesized products were characterized by X-ray diffraction, field emission scanning electronmicroscopy and room temperature photoluminescence measurement. The photocatalytic ac-tivity in degrading methyl orange was measured with a UV-Vis spectrophotometer. The pure ZnO microtubes exhibit an exact hexangular hollow structure with a diameter of about 700 nm, a length of 3 μm and a wall thickness of about 40 nm. The TiO₂-doped ZnO microtubes with TiO₂/ZnO ratio less than 5% have the same dimension with the pure ZnO microtubes, a smooth column shape, not a hexangular structure. The growth of ZnO may be inhibited by the more Ti⁴⁺ doped into ZnO structure to achieve a small dimension or a multiphase. The crystallinity of ZnO microtubes decreases with increasing TiO₂ content, and then a multiphase containing ZnO, Ti₃O₅ and TiO occur when the TiO₂/ZnO ratio is more than 5%. The UV emission intensity of the TiO₂-doped ZnO obviously increases and then tends to decrease with TiO₂/ZnO ratio increasing. The photocatalytic properties of the TiO₂-doped ZnO microtubes are very effcient in degrading organic dyes of methyl orange and are well identical with its PL properties and the crystallinity.     

Effect of annealing temperature on the structural and optical properties of Zn1−xMgxO particles prepared by oxalate precursor

Zn_1−xMg_xO particles were prepared using zinc and magnesium oxalate precursor by co-precipitated method. The lattice constants of Zn_1−xMg_xO proved that the interstitial Mg formed at 500 °C and Mg replaced Zn in ZnO tetrahedral coordination at 800 °C. Compared with the ZnO, the absorbing band edge of the Zn_1−xMg_xO displayed blue shifts. The room temperature photoluminescence was similar to ZnO and variation of Mg content did not change the shape or peak position of the emission spectra markedly when it was annealed at 500 °C. However, its blue emission band disappeared, and a relatively strong green light emission at 498 nm appeared after annealed at 800 °C. The photoluminescence intensity ratios I_(green)/I_(UV) of Zn_1−xMg_xO varied with Mg content and the green light emission peak shifted from 498 nm to 472 nm when Mg content increased from 0 to 2.0 at.%.     

[Bis(trispivalatodimolybdenum (II))-μ-bis(4′-carboxylato-2,2′:6′,2″-terpyridine) ruthenium (II)] (2+) Tetrafluoroborate: Photophysical Studies

The photophysical properties of the title compound have been studied by fs and ns transient absorption spectroscopy. The electronic absorption spectrum consists of three principle absorptions assigned to terpy ¹LLCT at ~300 nm, ruthenium (II) t_2g⁶ to terpy ¹MLCT at ~470 nm and Mo₂ δ to terpycarboxylate at ~670 nm. The compound shows weak room temperature emission in THF solution at ~1,100 nm when excited into each of the aforementioned bands. This emission is assigned to the T₁ state, ³MMδδ*. Transient absorption spectroscopy indicates a lifetime for T₁ of 9.6 μs. This paper is dedicated to Prof. C. N. R. Rao.     

Structural,optical and photoluminescence properties of Zn<Subscript>1−x</Subscript>Ce<Subscript>x</Subscript>O (x = 0, 0.05 and 0.1) nanoparticles by sol–gel method annealed under Ar atmosphere

Ce doped ZnO nanoparticles (Zn_1−xCe_xO, x = 0.0, 0.05 and 0.1) have been synthesized by sol–gel method at annealing temperature of 500 °C for 1 h under Ar atmosphere. The synthesized samples have been characterized by powder X-ray diffraction (XRD), energy dispersive X-ray studies, UV–Visible spectrophotometer and fourier transform infrared (FTIR) spectroscopy. The XRD measurements indicate that the prepared nanoparticles have a hexagonal wurtzite structure and CeO₂ crystallites. The calculated average crystalline varied from 21.97 to 15.62 nm with increase in Ce concentrations. The increase in lattice parameters reveals the substitution of Ce into ZnO lattice. The presence of functional groups and the chemical bonding is confirmed by FTIR spectra. PL spectra of the Zn_1−xCe_xO system show that the shift in near band edge emission from 386 to 363 nm and a shift in blue band emission from 517 to 485 nm which confirms the substitution of Ce into the ZnO lattice.     

Growth and characterization of ZnO (microdisks)/W18O49 (nanorods) heterostructures

ZnO (microdisks)/W₁₈O₄₉ (nanorods) heterostructures were grown on a Si(111) substrate using a thermal evaporation method. X-ray diffraction of the products indicated two separate phases belong to monoclinic W₁₈O₄₉ and hexagonal ZnO structures. Field emission scanning electron microscope (FESEM) images showed W₁₈O₄₉ nanorods with approximately uniform diameters (∼20 nm) on ZnO microdisk. Field emission Auger electron spectroscopy (FEAES) also confirmed two separate elemental characteristics of W₁₈O₄₉ and ZnO. The Raman and photoluminescence (PL) studies demonstrated that the ZnO microdisks have a good crystallinity with excellent optical properties. The Raman results of the ZnO(microdisks)/W₁₈O₄₉(nanorods) heterostructures indicated only W₁₈O₄₉ structure and the PL results of the heterostructures showed two peaks, one in the ultraviolet region at 374 nm and another in the visible region at 500 nm, which both belong to W₁₈O₄₉ nanorods.     

The effects of annealing temperature on structural and optical properties of S-doped ZnO nanobelts

In this study, the effects of thermal annealing temperature on the structural and optical properties of S-doped ZnO nanobelts were investigated. The XRD pattern shows that the crystallinity of S-doped ZnO nanobelts improves with increased annealing temperature. Room temperature photoluminescence spectroscopy of the as-grown S-doped ZnO nanobelts shows no detectable ultraviolet peak with the broad peaks in the visible emission region at 480, 505, and 518 nm. A weak peak in the ultraviolet region at 383 nm appears after annealing at 400 and 600 °C. Raman spectroscopy of the sample also shows a significant change with an increase in the annealing temperature.     

Nano-sized polycrystalline bismuth silicon oxide powder by sol–gel technique

Bismuth silicon oxide (Bi₁₂SiO₂₀, BSO) nano crystalline powder was prepared by sol–gel technique using bismuth nitrate and tetraethyl orthosilicate as starting materials. The prepared samples were sintered at various temperatures (750 °C maximum) and characteristic sillenite single cubic phase with crystallite size ~38 nm (calculated from room temperature powder XRD measurements) was realized at 750 °C sintering temperature. SEM analysis showed that the powder contains the nano-sized particles with almost spherical morphology. The observed frequencies in room temperature FTIR spectrum could be assigned to Bi–O, Si–O and Bi–O–Si bonds. The FWHM (full width at half maximum) of the diffraction peaks decreased while the intensity of FTIR absorption lines increased with the increase in the sintering temperature indicating better bond formation and crystallization. The thermograph of the samples recorded in the temperature range 50–1,000 °C showed almost no weight loss after ~575 °C further confirmed the conclusion arrived at from XRD and FTIR analysis. The samples sintered at 750 °C showed about 50% absorbance in 400–600 nm region which was consistent with the pale yellow color of the sample. Broad blue emission centered ~478 nm was observed when excited by 350 nm radiation from a Xe-lamp. The intensity of this broad emission band increased while its FWHM decreased with the increase in sintering temperature. Self-trapped excitons could be responsible for this emission.     

砷掺杂的ZnO纳米线的发光特性

在GaAs基底上制备了高质量的直径为10～100 nm、长度约几个微米的As掺杂ZnO纳米线. 扫描电镜、EDX分析及透射电镜分析显示, ZnO纳米线具有较好的晶态结构. 对As掺杂前后的ZnO纳米线进行光学特性测量, 结果表明, ZnO纳米线在385 nm处有较强的紫外发光峰, 在505 nm左右有较弱的蓝绿发光峰; As掺杂较大地改变了ZnO纳米线的发光性质, 使本征发光峰移到393 nm处, 蓝绿发光强度有了很大程度的提高.     

Optical and Structural Properties of Zn2SiO4:Mn2+ from SLS Waste Bottle Obtained by a Solid State Method

In this studies, 2 wt.% Mn-doped Zn₂SiO₄ were synthesized from SLS waste glass, ZnO and MnO using conventional solid-state method. Structural and optical properties were examined as functions of sintering temperature. Density and linear shrinkage of samples increased with increasing in sintering temperature. X-Ray Diffraction pattern revealed that sintering temperature play an important role in enhancing crystallization of Zn₂SiO₄. It was found that the phase formation changed from amorphous to ȕ- Zn₂SiO₄ and then to α-Zn₂SiO₄ with the unsintered to sinter at 600 °C and 700 °C respectively. The morphology under FESEM characterization shows that the samples become more uniform with rectangular shape like as the sintering temperature increased. From UV-Vis spectroscopy, the results obtained showed that the intensive absorption occurred in the UV region, in the range of 250-γλ0 nm. Prominent green emission colours of α-Zn₂SiO₄ were observed centred at 527 nm while the yellow emission centred at η8η nm resulted from ȕ-Zn₂SiO at an excitation of 260 nm. However, red emission centred at 600 nm was observed for glass samples. These emissions come from the Mn-dopant and correspond to the ⁴T₁ – ⁶A₁ transition.     

Preparation,characterization and activity evaluation of p–n junction photocatalyst p-NiO/n-ZnO

In this paper, p–n junction photocatalyst NiO/ZnO was prepared by the sol–gel method using Ni (NO₃)₂ and zinc acetate as the raw materials. The structural and optical properties of the p–n junction photocatalyst NiO/ZnO were characterized by X-ray photoelectron spectroscopy (XPS), X-ray powder diffraction (XRD), scanning electron microscopy (SEM), Brunauer–Emmett–Teller (BET) analysis, UV–Vis diffuse reflection spectrum (DRS) and the fluorescence emission spectra. The photocatalytic activity of the photocatalyst was evaluated by photocatalytic reduction of Cr₂O₇ ²⁻ and photocatalytic oxidation of methyl orange (MO). The results showed that the photocatalytic activity of the p–n junction photocatalyst NiO/ZnO is much higher than that of ZnO on the photocatalytic reduction of Cr₂O₇ ²⁻. However, the photocatalytic activity of the photocatalyst is much lower than that of ZnO on the photocatalytic oxidation of methyl orange. Namely, the p–n junction photocatalyst NiO/ZnO has higher photocatalytic reduction activity, but lower photocatalytic oxidation activity. The heat treatment condition also influences the photocatalytic activity strongly, and the best preparation condition is about 400 °C for 2 h. Effect of the heat treatment condition on the photocatalytic activity of the photocatalyst was also investigated. The mechanisms of influence on the photocatalytic activity were discussed by the p–n junction principle.     

The particle dimension controlling synthesis of α-MnO2 nanowires with enhanced catalytic activity on the thermal decomposition of ammonium perchlorate

Hydrothermal method synthesis of α-MnO₂ nanowires has been achieved at different temperatures in this work. X-ray diffraction and transmission electron microscopy confirmed the pure phase of the α-MnO₂ nanowires. All of the samples crystallized in a single-phase nanowires shape. The α-MnO₂ nanowires diameter increased from 11 nm to 21 nm with the increase in hydrothermal temperature from 120 °C to 200 °C. The α-MnO₂ catalytic activity on the decomposition of ammonium perchlorate (AP) was characterized through thermogravimetric analysis. The decomposition rate of AP with the addition of α-MnO₂ was size relative. The 11 nm MnO₂ nanowires exhibited the best catalytic activity, which lowered the high-temperature peak of AP by 130 °C.     

Zinc nanowires synthesized on a large scale by a simple carbothermal process

Metallic Zn nanowires have been synthesized by a new carbothermal reduction route in which ZnO and Eucalyptus sp. tar pitch were used as source materials. This simple practical procedure was capable of producing Zn nanowires in large quantities without reoxidation. This process was carried out in inert atmosphere, without vacuum or catalyst, at temperatures (800–900 °C) lower than those required in the carbothermal reduction of ZnO with graphite. A comparative study was performed using graphite that is traditionally used as a ZnO reducer, under the same experimental conditions, however, no reaction was observed. The new process involves the pyrolysis of biopitch to obtain a highly reactive coke and the reduction of ZnO with the release of Zn_(v) for the growth of Zn_(s) nanowires. The resulting Zn nanowires were characterized by X-ray diffractometry, energy-dispersive spectroscopy and scanning electron microscopy. Differential thermal analysis and thermogravimetric analysis coupled with infrared analysis techniques were used in an effort to understand the underlying mechanism and establish the best ratio biopitch/ZnO to be used. This paper presents the characterization of the as-synthesized nanowires and discusses the main reactions involved in their production.     

ZnO纳米线形态对其光致发光性能的影响

以多孔氧化铝膜为模板,电化学沉积出Zn纳米线,再通过高温氧化得到ZnO纳米线阵列。通过改变制备多孔氧化铝模板的工艺参数来改变模板纳米孔径,进而改变ZnO纳米线的直径,得到不同形态的ZnO纳米线阵列。应用X射线衍射仪、透射电子显微镜测试技术表征了ZnO纳米线的结构与形貌。结果发现,X射线衍射时会出现随ZnO纳米线直径增大衍射峰增多和增强的现象。采用荧光光谱仪测试样品的光致发光性能,通过Gaussian原理对谱峰的拟合分析了ZnO纳米线形态对其光致发光光谱的影响。结果表明,随着纳米线直径从30nm至60nm依次增大,其结晶性和化学计量比逐渐变好。近紫外区和蓝光区的发射峰随着纳米线直径的增大而蓝移,而纳米线直径为60nm的样品则出现随直径增大而红移的现象。结果可见,直径在55~60nm间的某点将是ZnO纳米线的结构和光致发光性能变化的临界点。     

ZnO-聚苯胺同轴纳米线及其列阵的制备和表征

以阳极氧化铝膜 (AAO)作模板 ,制备聚苯胺 (PANI)纳米管和PANI纳米管列阵 ;同时利用溶胶_凝胶法制备ZnO_PANI同轴纳米线和同轴纳米线列阵 .PANI纳米管和ZnO_PANI同轴纳米线的形貌通过透射电子显微镜表征 .PANI纳米管的外径约 3 0nm ,内径约 1 0nm ;ZnO_PANI同轴纳米线直径约 60nm .实验发现 ,较之ZnO纳米线 ,同轴AAO模板中纳米线列阵的可见光发射谱带兰移 ,强度显著增强 ,这可能和PANI链上的NH基团与表面Zn2 +离子之间的相互作用有关 ,以及由于ZnO纳米微粒在PANI上富集、PANI的光生载流子部分转移给ZnO微粒所致 .实验还发现分散在NaOH溶液中的同轴纳米线 ,其可见光发射谱带比AAO模板中同轴纳米线的谱带兰移更甚